A Carbon Molecular Sieve Membrane-Based Reactive
Separation Process for Pre-Combustion CO2 Capture
Mingyuan Cao1, Linghao Zhao1, Dongwan Xu1, Seçgin Karagöz2, Patricia Pichardo2, Richard J. Ciora, Jr.3, Doug Parsley3, Paul K.T. Liu3,
Vasilios I. Manousiouthakis2, and Theodore T. Tsotsis1
1Mork Family Department of Chemical Engineering and Materials Science, University of Southern California; 2Chemical and Biomolecular Engineering Department,
University of California; 3Media and Process Technology, Inc.
Key Technology Components
Multi-Scale MR-AR Model for Process Scale-Up
Technology BackgroundMembrane Reactor Studies
The CMSM employed demonstrated robust and stable performance during the long-term run (>500 hr at T=250°C and P=25 bar)
Adsorption-enhanced WGS membrane reactor (MR-AR) process for
pre-combustion CO2 capture
Advantages
➢ No syngas
pretreatment required
➢ Improved WGS
efficiency
➢ Significantly reduced
catalyst weight usage
requirements
➢ Efficient H2
production, and
superior CO2
recovery and purity
Conventional IGCC Power Plant
Carbon Molecular Sieve (CMS) Membranes
Hydrotalcite (HTC) Adsorbent
High-Pressure Adsorption Isotherm at 250oC
1
10
100
1000
0 50 100 150 200 250 300 350 400 450
Per
mea
nce
[G
PU
]
Cumulative Syngas Exposure Time [hours]
#7 Helium #22 Helium #37 Helium
#7 Nitrogen #22 Nitrogen #37 Nitrogen
He or N2 Test Conditions
Pressure: 20 to 50 psig
Temperature: 230 to 265oC
Part ID He
[GPU]
N2
[GPU]
H2
[GPU]
CO2
[GPU]
H2/N2
[-]
H2/CO2
[-]
HMR-61 578 2.5 550 1.0 219 558
HMR-67 450 1.6 581 2.8 354 211
HMR-68 591 3.0 675 2.7 227 248
MR-70 445 1.5 502 0.7 344 738
HMR-72 500 1.7 602 2.5 359 246
HMR-104 542 1.5 540 2.0 361 270
Lab-Scale Experimental Set-Up
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
0
1
2
3
4
5
6
7
8
9
10
11
12
Pressure (bar)
Exc
ess
so
rptio
n (
wt%
/g)
Before correcting
After correcting
Co-Mo/Al2O3 Sour-Shift Catalyst
Field-tested at NCCC
Reaction rate data generated and global kinetics model developed
0
10
20
30
40
50
60
70
80
0 20 40 60 80
Sim
ula
ted C
O c
onver
sion
Measured CO conversion
−𝑟𝑐𝑜= 𝐴 𝑒−𝐸𝑅𝑇 𝑝𝑐𝑜
𝑎 𝑝𝐻2𝑂𝑏 𝑝𝑐𝑜2
𝑐 𝑝𝐻2𝑑 1 − 𝛽
𝛽 =1
𝐾𝑒𝑞
൫𝑃𝐶𝑂2 . 𝑃𝐻2 )
൯ሺ𝑃𝐶𝑂 . 𝑃𝐻2𝑂
𝐾𝑒𝑞 = ex p4577.8
𝑇− 4.33
Lab-Scale Experiments
AR Studies
CO in the AR and total MR-AR conversion, and species molar flow rates. (Left Top) AR I,
first cycle, (Right Top) AR II, first cycle, (Left Bottom) AR I, second cycle, (Right Bottom)
AR II, second cycle. Temp.=250 °C, pressure=25 bar, H2O/CO ratio=2.8, W/FCO=55
g·h/mol.
Solid Phase
Fluid Phase
Adsorbent Pellet
Fluid Phase
Catalyst Pellet
Adsorbent PelletCatalyst Pellet
Fluid Phase
Syngas Water
Carbon Depleted Syngas
Carbon Depleted
Syngas
Water
Reaction Zone
Permeation Zone
J,j
Fluid Phase
Pellet
2 2 2CO HO CO H⎯⎯→+ +⎯⎯
Catalyst Pellet
Sweep (H2O)
J,j
J,j
J,j
J,j
J,j
J,j
J,j
CH4, H2, CO, CO2, H2O
2 2 2CO HO CO H⎯⎯→+ +⎯⎯
ADSORPTION
REGENERATION
Water+CO2
Water+CO2
CO2>= 20 bar
CO2 Drying andCompression
CO2 to storage 150 bar
Preliminary TEA - MR-AR IGCC Process Scheme
Field-Scale Study of the MR-AR Process
The MR-AR model accounts for mass/energy balances in the catalyst, sorbent and the reactor fluid phases. The
Dusty-Gas-Model is used to describe membrane transport. It describes well the laboratory data without resorting
to adjustable parameters. It is used in the TEA calculations.
Uky-CAER Gasifier
AcknowledgementThe financial support of the U.S. Department of Energy (FE0026423
and F0037137), the technical guidance and assistance of our Project
Manager Andrew Jones, and helpful discussions with Ms. Lynn
Brickett are gratefully acknowledged. MR-AR Skid
Top Related